Seven novel bismuth(III)-halide phases, Bi2Cl6(terpy)2·0.5(H2O) (1), Bi2Cl4(terpy)2(k2-TC)2(2) (TC = 2-thiophene monocarboxylate), BiCl(terpy)(k2-TC)2 (3A-Cl), BiBr(terpy)(k2-TC)2 (3A-Br), BiCl(terpy)(k2-TC)2 (3B-Cl), [BiCl(terpy)(k2-TC)2][Bi(terpy)(k2-TC)3]·0.55(TCA) (4), [BiBr3(terpy)(MeOH)] (5), and [BiBr2(terpy)(k2-TC)][BiBr1.16(terpy)(k2-TC)1.84] (6), were prepared under mild synthetic conditions from methanolic/aqueous solutions containing BiX3 (X = Cl, Br) and 2,2':6',2″-terpyridine (terpy) and/or 2-thiophene monocarboxylic acid (TCA). A heterometallic series, 3A-Bi1-xEuxCl, with the general formula Bi1-xEuxCl(terpy)(k2-TC)2 (x = 0.001, 0.005, 0.01, 0.05) was also prepared through trace Eu doping of the 3A-Cl phase. The structures were determined through single-crystal X-ray diffraction and are built from a range of molecular units including monomeric and dimeric complexes. The solid-state photoluminescent properties of the compounds were examined through steady-state and time-resolved methods. While the homometallic phases exhibited broad green to yellow emission, the heterometallic phases displayed yellow, orange, and red emission that can be attributed to the simultaneous ligand/Bi-halide and Eu centered emissions. Photoluminescent color tuning was achieved by controlling the relative intensities of these concurrent emissions through compositional modifications including the Eu doping percentage. Notably, all emissive homo- and heterometallic phases exhibited rare visible excitation pathways that based on theoretical quantum mechanical calculations are attributed to halide-metal to ligand charge transfer (XMLCT). Through a combined experimental and computational approach, fundamental insight into the structure-property relationships within these Bi halide organic hybrid materials is provided.